Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/14—Copolymers of propene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/14—Copolymers of propene
  • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
  • B32B2038/0028—Stretching, elongating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
  • B32B2250/242—All polymers belonging to those covered by group B32B27/32
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/514—Oriented
  • B32B2307/518—Oriented bi-axially
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/704—Crystalline
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/718—Weight, e.g. weight per square meter
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/72—Density
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
  • B32B2309/02—Temperature
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2323/00—Polyalkenes
  • B32B2323/04—Polyethylene
  • B32B2323/043—HDPE, i.e. high density polyethylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C08L57/02—Copolymers of mineral oil hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/91—Product with molecular orientation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2813—Heat or solvent activated or sealable
  • Y10T428/2817—Heat sealable
  • Y10T428/2826—Synthetic resin or polymer

Definitions

• the invention relates to a polypropylene multilayer film which comprises at least one base layer containing polypropylene or a polypropylene mixture and resin, and at least one cover layer which contains a mixture or a blend of two components I and II.
• Component I of the mixture or blend is a propylene homopolymer or a copolymer of ⁇ -olefins with 2 to 10 carbon atoms or a terpolymer of ⁇ -olefins with 2 to 10 carbon atoms or a mixture of two or more of the homo-, co- and terpolymers or a blend of two or more of the homopolymers, copolymers and terpolymers mentioned.
• Component II of the mixture or blend is a high density polyethylene (HDPE) or a blend of HDPE and one or more other polymers, selected from the group consisting of propylene homopolymer, copolymer of ⁇ -olefins with 2 to 10 carbon atoms, terpolymer of ⁇ - Olefins with 2 to 10 carbon atoms, and a blend of copolymers and terpolymers of ⁇ -olefins with 2 to 10 carbon atoms.
• HDPE high density polyethylene
• HDPE high density polyethylene
• one or more other polymers selected from the group consisting of propylene homopolymer, copolymer of ⁇ -olefins with 2 to 10 carbon atoms, terpolymer of ⁇ - Olefins with 2 to 10 carbon atoms, and a blend of copolymers and terpolymers of ⁇ -olefins with 2 to 10 carbon atoms.
• the film according to the invention is characterized by a characteristic matt surface or appearance and good twist behavior.
• the invention further relates to a method for producing the multilayer film and its use.
• a special type of closure of full wraps for the purpose of packaging packaging goods is turning or wrapping.
• This method of packaging is known, in particular for the full wrapping of smaller packaging goods, with round or approximately round objects such as candies, bottles, candles, drops rolls, chocolate and marzipan bars, Easter eggs or the like often being packaged in this way.
• cellulose i.e. regenerated cellulose, non-oriented polypropylene or PVC film
• PVC polypropylene
• EP-A-0 479 101 relates to a multilayer, highly transparent, biaxially oriented polypropylene film with very good twist properties, which is particularly suitable for turning wrapping.
• the film is characterized in that the base layer consists of 70 to 95% by weight of polypropylene and 5 to 30% by weight of a low molecular weight hydrocarbon resin with a softening point of 130 to 180 ° C and the cover layers an antiblocking agent with an average particle size have from 2 to 5 ⁇ m and may be equipped with a polydimethylsiloxane.
• the cover layers have a maximum thickness of 0.5 ⁇ m.
• the films are further characterized by high mechanical properties that are approximately the same size in the longitudinal and transverse directions. The film is oriented in a balanced manner.
• EP-A-0 432 452 relates to a transparent wrapping film made of polypropylene, which is monoaxially oriented and has a permanent elongation transversely to the orientation direction of greater than 45%.
• the film can optionally be provided with one or more cover layers made of conventional cover layer materials.
• DE-A-35 35 472 describes a film which is also well suited for turning. By adding siloxane and antiblocking agent to the top layers, the film gets the desired processing properties on high-speed rotary wrapping machines.
• a disadvantage of the film is the relatively high resin content, which is required for the good turning impact. 25% by weight is given as an example. This increases the cost of the film drastically.
• the known rotary wrapping films are in need of improvement with regard to their appearance, with regard to their processing properties and in particular with regard to their scratch resistance. Wrapping films with a conventional base layer and conventional C2 / C3 copolymer top layer often show cloudy structures or optical inhomogeneities.
• German patent application P 41 35 096.0 discloses polyolefin multilayer films made of a polypropylene base layer and a top layer made of an HDPE blend.
• This HDPE blend consists of HDPE and co- and / or terpolymers made of ⁇ -olefins and optionally polypropylene.
• the top layer of the multilayer film has a minimum gloss and a maximum haze, which gives the film a characteristic matt appearance.
• a biaxially oriented polyolefin multilayer film is known from US Pat. No. 4,578,316, the base layer of which consists of a polypropylene homopolymer and the top layer of which is a blend of polypropylene and MDPE and / or HDPE.
• This polyolefin film has a low coefficient of friction in conjunction with an easily wettable surface; however, this film also has excellent optical transparency.
• WO 89/10839 describes polyolefin multilayer films whose base layer consists of a propylene polymer and whose cover layers consist either of HDPE or an ethylene-propylene copolymer or a polypropylene, the film being stretched under special temperature conditions. In particular, it has a low coefficient of friction and good wettability, but at the same time it also has a high gloss and low haze.
• EP-A-0 367 613 discloses a multilayer film comprising a vacuole-containing polypropylene base layer and a cover layer which can be written on and contains a first polymer with a melt flow index of ⁇ 1 g / 10 min and a second polymer which is compatible with said first polymer is incompatible.
• An HDPE with a density of 0.92 to 0.97 g / cm 3 is described as an example of the first polymer.
• the incompatible polymer is a polypropylene or copolymers of polypropylene or terpolymers of polypropylene.
• the film described has an opaque appearance, ie it is essentially opaque. It is described that the film has a matt appearance when it is printed.
• the SiO2-containing cover layer has a high mattness which gives the film a paper-like appearance.
• the film described has a density of 0.69 g / cm3.
• the matt, SiO2-containing surface proves to be in need of improvement when printed.
• the color shows a gray veil and not a uniform appearance. This is attributed to inhomogeneities in the film itself due to its opacity not appear as strong, but come out when printed.
• the printed foils are stained and are not accepted by the processor.
• the films known from the prior art with an HDPE-modified cover layer are not suitable as a wrapping film due to their mechanical properties.
• the appearance of the foils is in need of improvement.
• the object of the present invention was to provide a multilayer film which is suitable for turning wrapping and is characterized by a matt appearance on at least one surface and at the same time has good scratch resistance.
• the gloss of the surface / s should be optimized with regard to this desired matt characteristic.
• a homogeneous film look without spotty or streaky imperfections and without a cloud structure is important.
• a uniform appearance of the printing is required.
• the film should have good twist behavior for turning and good running properties.
• component I essentially a propylene homopolymer or a copolymer of Ethylene and propylene or Ethylene and butylene or Propylene and butylene or Ethylene and another ⁇ -olefin having 5 to 10 carbon atoms or Propylene and another ⁇ -olefin having 5 to 10 carbon atoms or a terpolymer of Ethylene and propylene and butylene or Ethylene and propylene and another ⁇ -olefin having 5 to 10 carbon atoms or a mixture of two or more of the homopolymers, copolymers and terpolymers mentioned or a blend of two or more of the homopolymers, copolymers and terpolymers mentioned, optionally mixed with one or more of the homopolymers, copolymers and terpolymers mentioned, contains and component II essentially contains an HDPE or a blend of
• Mixtures for the purposes of the present invention are understood to mean mechanical mixtures which are produced from the individual components.
• the individual components are pressed as small size molded articles, for. B. lenticular, spherical or rod-shaped granules, poured together and mixed mechanically with a suitable vibrating device.
• a blend in the sense of the present invention is an alloy-like composite of the individual components, which can no longer be broken down into the original components.
• a blend has properties like a homogeneous substance and can be characterized accordingly by suitable parameters.
• the base layer of the multilayer film according to the invention essentially contains a propylene polymer or a polypropylene mixture and resin.
• the propylene polymer of the base layer contains for the most part (at least 90%) propylene and has a melting point of 140 ° C. or higher, preferably 150 to 170 ° C.
• Isotactic homopolypropylene with an n-heptane soluble content of 6% by weight or less based on the isotactic homopolypropylene, copolymers of ethylene and propylene with an ethylene content of 10% by weight or less, copolymers of propylene with C4-C8- ⁇ - Olefins with an ⁇ -olefin content of 10% by weight or less are preferred propylene polymers for the base layer, with isotactic homopolypropylene being particularly preferred.
• the propylene polymer of the core layer generally has a melt flow index of 0.5 g / 10 min to 8 g / 10 min, preferably 2 g / 10 min to 5 g / 10 min, at 230 ° C and a force of 21.6 N ( DIN 53 735).
• Dialkyl peroxides are particularly preferred as organic peroxides, an alkyl radical being understood to mean the customary saturated straight-chain or branched lower alkyl radicals having up to six carbon atoms.
• an alkyl radical being understood to mean the customary saturated straight-chain or branched lower alkyl radicals having up to six carbon atoms.
• 2,5-dimethyl-2,5-di (t-butylperoxy) hexane or di-t-butyl peroxide are preferred.
• the base layer of the film according to the invention contains a resin, generally in an amount of 5 to 40% by weight, preferably 10 to 40% by weight, in particular 15 to 35% by weight, based on the weight of the base layer.
• a resin generally in an amount of 5 to 40% by weight, preferably 10 to 40% by weight, in particular 15 to 35% by weight, based on the weight of the base layer.
• Low molecular weight resins in particular hydrocarbon resins, are preferred as resins.
• the hydrocarbon resins can be partially or fully hydrogenated.
• synthetic resins or resins of natural origin can be considered as resins. It has proven to be particularly advantageous to use resins with a softening point of ⁇ 80 ° C (measured according to DIN 1995-U4 or ASTM E-28), those with a softening point of 100 to 180 ° C, in particular 120 to 160 ° C, are preferred.
• the resin is incorporated into the film (e.g. single-screw or cascade extruder) preferably in the form of a masterbatch, which is added to the extruder.
• masterbatches containing 30 to 70% by weight, preferably 50% by weight, of propylene homopolymer and 70 to 30% by weight, preferably 50% by weight, of hydrocarbon resin are customary. The percentages by weight relate to the total weight of propylene polymer and hydrocarbon resin.
• hydrocarbon resins are preferred, namely in the form of petroleum resins (petroleum resins), styrene resins, cyclopentadiene resins and terpene resins (these resins are described in Ullmanns Encyklopadie der techn. Chemie, 4th edition, volume 12, pages 525 to 555).
• the petroleum resins are those hydrocarbon resins which are produced by polymerizing deep-decomposed petroleum materials in the presence of a catalyst. These petroleum materials usually contain a mixture of resin-forming substances such as styrene, methylstyrene, vinyltoluene, indene, methylindene, butadiene, isoprene, piperylene and pentylene.
• the styrene resins are low molecular weight homopolymers of styrene or copolymers of styrene with other monomers such as methyl styrene, vinyl toluene and butadiene.
• the cyclopentadiene resins are cyclopentadiene homopolymers or cyclopentadiene copolymers obtained from coal tar distillates and decomposed petroleum gas. These resins are made by keeping the materials containing cyclopentadiene at a high temperature for a long time. In Depending on the reaction temperature, dimers, trimers or oligomers can be obtained.
• the terpene resins are polymers of terpenes, i.e. H. Hydrocarbons of the formula C10H16, which are contained in almost all essential oils or oil-containing resins of plants, and phenol-modified terpene resins. Pinene, ⁇ -pinene, dipentene, limonene, myrcene, camphene and similar terpenes can be mentioned as specific examples of the terpenes.
• Styrene homopolymers, styrene copolymers, cyclopentadiene homopolymers, cyclopentadiene copolymers and / or terpene polymers with a softening point in each case above 100 ° C. are also used as hydrocarbon resins (the hydrogenated product is preferred for the unsaturated polymers).
• the cyclopentadiene polymers with a softening point of 140 ° C. and above in the base layer are very particularly preferably used.
• the hydrocarbon resins can also be the so-called modified hydrocarbon resins.
• the modification is generally carried out by reacting the raw materials before the polymerization, by introducing special monomers or by reacting the polymerized product, in particular hydrogenations or partial hydrogenations being carried out.
• At least one cover layer of the multilayer film according to the invention contains a mixture or a blend of two components I and II, which are described in more detail below, and optionally added additives.
• Component I of the top layer mixture or blend essentially contains a propylene homopolymer or a copolymer of Ethylene and propylene or Ethylene and butylene or Propylene and butylene or Ethylene and another ⁇ -olefin having 5 to 10 carbon atoms or Propylene and another ⁇ -olefin having 5 to 10 carbon atoms or a terpolymer of Ethylene and propylene and butylene or Ethylene and propylene and another ⁇ -olefin having 5 to 10 carbon atoms or a mixture of two or more of the homopolymers, copolymers and terpolymers mentioned or a blend of two or more of the homopolymers, copolymers and terpolymers mentioned, optionally mixed with one or more of the homopolymers, copolymers and terpolymers mentioned.
• Component I particularly preferably consists essentially of a propylene homopolymer or a copolymer of Ethylene and propylene or Ethylene and butylene-1 or Propylene and butylene-1 or from a terpolymer of Ethylene and propylene and butylene-1 or from a mixture of two or more of the particularly preferred homopolymers, copolymers and terpolymers mentioned or of a blend of two or more of the particularly preferred homopolymers, copolymers and terpolymers mentioned, optionally mixed with one or more of the homopolymers, copolymers and terpolymers mentioned, in particular propylene homopolymer or statistical ethylene-propylene copolymers with an ethylene content of 2 to 10% by weight, preferably 5 to 8% by weight, or statistical propylene-butylene-1 copolymers with a butylene content of 4 to 25% by weight, preferably 10 to 20% by weight, each based on the total weight of the copolymer
• the propylene homopolymer used as or in component I contains for the most part (at least 90%) propylene and has a melting point of 140 ° C. or higher, preferably 150 to 170 ° C., isotactic homopolypropylene with an n-heptane-soluble fraction of 6% by weight. % and less, based on the isotactic homopolypropylene, is preferred.
• the homopolymer of component I or the homopolymer contained therein generally has a melt flow index of 0.5 g / 10 min to 15 g / 10 min, preferably 1.5 g / 10 min to 6 g / 10 min, at 230 ° C and a force of 21.6 N (DIN 53 735).
• Component II of the top layer mixture or blend essentially contains an HDPE or a blend which essentially comprises HDPE as blend component A and a blend component B.
• the HDPE as component II and HDPE as blend component A are selected from the polyethylenes described above, so that the same HDPE as blend component A is in principle possible as component II, but need not be identical.
• the blend component B consists essentially of a propylene homopolymer or a copolymer of Ethylene and propylene or Ethylene and butylene or Propylene and butylene or Ethylene and another ⁇ -olefin having 5 to 10 carbon atoms or Propylene and another ⁇ -olefin having 5 to 10 carbon atoms or from a terpolymer of Ethylene and propylene and butylene or Ethylene and propylene and another ⁇ -olefin of 5 to 10 carbon atoms or from a mixture of two or more of the homopolymers, copolymers and terpolymers mentioned or of a blend of two or more of the homopolymers, copolymers and terpolymers mentioned.
• the blend component B particularly preferably consists essentially of a propylene homopolymer or a copolymer of Ethylene and propylene or Ethylene and butylene-1 or Propylene and butylene-1 or from a terpolymer of Ethylene and propylene and butylene-1 or from a mixture of two or more of the particularly preferred homopolymers, copolymers and terpolymers mentioned or of a blend of two or more of the particularly preferred homopolymers, copolymers and terpolymers mentioned, wherein in particular propylene homopolymer or statistical ethylene-propylene copolymers with an ethylene content of 2 to 10% by weight, preferably 5 to 8% by weight, or statistical propylene-butylene-1 copolymers with a butylene content of 4 to 25% by weight, preferably 10 to 20% by weight, each based on the total weight of the copolymer, or statistical ethylene-propylene-butylene-1-terpolymers an ethylene content
• the propylene homopolymer used as or in blend component B contains for the most part (at least 90%) propylene and has a melting point of 140 ° C. or higher, preferably 150 to 170 ° C., isotactic homopolypropylene with an n-heptane-soluble fraction of 6% by weight. % and less, based on the isotactic homopolypropylene, is preferred.
• the homopolymer of blend component B or the homopolymer contained therein generally has a melt flow index of 0.5 g / 10 min to 15 g / 10 min, preferably 1.5 g / 10 min to 6 g / 10 min, at 230 ° C and a force of 21.6 N (DIN 53 735).
• the blend of components A and B has a melt flow index (DIN 53 735 at 230 ° C and 21.6 N load) of 1.5 g / 10 min to 12 g / 10 min, preferably 2.5 g / 10 min to 6 g / 10 min, the melt flow index of the blend preferably being higher than that of the propylene polymer of the base layer.
• a melt flow index (DIN 53 735 at 230 ° C and 21.6 N load) of 1.5 g / 10 min to 12 g / 10 min, preferably 2.5 g / 10 min to 6 g / 10 min, the melt flow index of the blend preferably being higher than that of the propylene polymer of the base layer.
• the melting range of the blend is between 100 and 160 ° C, preferably between 120 and 150 ° C.
• the ratio (weight ratio) of the two components I and II of the cover layer mixture or of the blend can vary within wide limits and depends on the intended use of the multilayer film.
• the multilayer film according to the invention comprises at least the resin-containing base layer described above and at least one matt cover layer which contains the mixture described above. Depending on its intended use, the multilayer film can have a further cover layer on the opposite side. If necessary, one or more intermediate layers can also be applied between the base layer and the cover layer (s).
• Preferred embodiments of the multilayer film have three layers.
• the structure, thickness and composition of a second cover layer can be selected independently of the existing matt cover layer according to the invention are, wherein the second cover layer may also contain one of the mixtures described above, which does not have to be identical to that of the first cover layer.
• the second cover layer can also contain any other common cover layer polymer.
• the thickness of the cover layer (s) is greater than 0.3 ⁇ m and is preferably in the range from 0.8 to 10 ⁇ m, in particular 1 to 5 ⁇ m, it being possible for cover layers on both sides to be of the same or different thickness.
• the total thickness of the polyolefin multilayer film according to the invention can vary within wide limits and depends on the intended use. It is preferably 5 to 100 ⁇ m, in particular 10 to 80 ⁇ m, the base layer making up approximately 50 to 95% of the total film thickness.
• the density of the film is generally 0.9 g / cm2 or above, preferably in the range of 0.9 to 0.95 g / cm2.
• At least one surface of the film can be corona or flame treated, the corresponding treatment optionally being carried out on both surfaces and being the same or different.
• both the base layer and the top layer (s) can contain further additives in an effective amount, preferably antistatic agents and / or antiblocking agents and / or lubricants and / or stabilizers and / or neutralizing agents are compatible with the propylene polymers of the base layer and the top layer / s, with the exception of the antiblocking agents, which are generally incompatible. All quantities in the following version in percent by weight (% by weight) in each case relate to the layer or layers to which the additive can be added.
• Preferred antistatic agents are alkali alkane sulfonates, polyether-modified, i.e. H. ethoxylated and / or propoxylated polydiorganosiloxanes (polydialkylsiloxanes, polyalkylphenylsiloxanes and the like) and / or the essentially straight-chain and saturated aliphatic, tertiary amines with an aliphatic radical having 10 to 20 carbon atoms, which with ⁇ -hydroxy- (C1-C4) -alkyl- Groups are substituted, with N, N-bis (2-hydroxyethyl) alkylamines having 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, being particularly suitable in the alkyl radical.
• the effective amount of antistatic is in the range of 0.05 to 0.3% by weight.
• glycerol monostearate is used in an amount of 0.03% to 0.2%, preferably as an antistatic.
• Suitable antiblocking agents are inorganic additives such as silicon dioxide, calcium carbonate, magnesium silicate, aluminum silicate, calcium phosphate and the like and / or incompatible organic polymers such as polyamides, polyesters, polycarbonates and the like, benzoguanamine formaldehyde polymers, silicon dioxide and calcium carbonate are preferred.
• the effective amount of antiblocking agent is in the range of 0.1 to 2% by weight, preferably 0.1 to 0.5% by weight.
• the average particle size is between 1 and 6 ⁇ m, in particular 2 and 5 ⁇ m, particles with a spherical shape, as described in EP-A-0 236 945 and DE-A-38 01 535, being particularly suitable.
• the antiblocking agents are preferably added to the cover layers.
• Lubricants are higher aliphatic acid amides, higher aliphatic acid esters, waxes and metal soaps as well as polydimethylsiloxanes.
• the effective amount of lubricant is in the range of 0.01 to 3% by weight, preferably 0.05 to 1% by weight.
• a particularly suitable aliphatic acid amide is erucic acid amide.
• polydimethylsiloxanes in the range from 0.05 to 2.0% by weight is preferred, in particular polydimethylsiloxanes with a viscosity of 10,000 to 1,000,000 mm 2 / s.
• the addition of the polydimethylsiloxanes into one or both outer layers is particularly favorable.
• the usual stabilizing compounds for ethylene, propylene and other ⁇ -olefin polymers can be used as stabilizers.
• the amount added is between 0.05 and 2% by weight.
• Phenolic stabilizers, alkali / alkaline earth stearates and / or alkali / alkaline earth carbonates are particularly suitable.
• Phenolic stabilizers are preferred in an amount of 0.1 to 0.6% by weight, in particular 0.15 to 0.3% by weight, and with a molar mass of more than 500 g / mol.
• Pentaerythrityl tetrakis-3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate or 1,3,5-trimethyl-2,4,6-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) benzene are particularly advantageous.
• Neutralizing agents are preferably calcium stearate and / or calcium carbonate and / or synthetic dihydrotalcite (SHYT) with an average particle size of at most 0.7 ⁇ m, an absolute particle size of less than 10 ⁇ m and a specific surface area of at least 40 m2 / g.
• SHYT synthetic dihydrotalcite
• the invention further relates to a method for producing the multilayer film according to the invention by the coextrusion method known per se.
• the procedure is such that the melts corresponding to the individual layers of the film are coextruded through a flat die, and the film thus obtained is solidified on one or more Roller (s) is pulled off, the film is subsequently biaxially stretched (oriented), the biaxially stretched film is heat-set and, if appropriate, is corona-treated on the surface layer provided for the corona treatment.
• the biaxial stretching (orientation) is generally carried out in succession, with the successive biaxial stretching, in which stretching first lengthwise (in the machine direction) and then transversely (perpendicular to the machine direction) being preferred.
• the polymer or the polymer mixture of the individual layers is compressed and liquefied in an extruder, it being possible for the additives which may have been added to be present in the polymer or in the polymer mixture or to be added to the extruder during the extrusion.
• the resins in particular are preferably added in the form of a masterbatch.
• the melts are then simultaneously pressed through a flat die (slot die), and the pressed multilayer film is drawn off on one or more take-off rolls, as it cools and solidifies.
• the film thus obtained is then stretched longitudinally and transversely to the direction of extrusion, which leads to an orientation of the molecular chains.
• the conditions in the longitudinal and in the transverse direction are selected such that the film is oriented approximately balanced in the longitudinal and transverse directions and has largely isotropic mechanical properties.
• the ratio of permanent elongation or tensile strength in the transverse direction to permanent elongation or tensile strength in the longitudinal direction is a maximum of 2.0.
• the prerequisites for achieving very good twist properties are then particularly favorable.
• the longitudinal aspect ratios according to the invention are 5.5 to 9, preferably 6 to 8.0.
• the transverse stretching ratios must also be selected. This preferably results in a range from 6.0 to 8.0.
• the film is expediently not stretched vertically, as is the case with other packaging films.
• a ratio of the stretching ratios of transverse / longitudinal of less than 2, preferably less than 1.5 must be maintained. This ratio is particularly preferably in the range from 0.5 to 1.5.
• the longitudinal stretching is expediently carried out with the aid of two rollers running at different speeds in accordance with the desired stretching ratio, and the transverse stretching with the aid of a corresponding tenter frame.
• the biaxial stretching of the film is followed by its heat setting (heat treatment), the film being held at a temperature of 140 to 160 ° C. for about 0.5 to 10 s.
• the film is then wound up in a conventional manner using a winding device.
• the temperatures at which longitudinal and transverse stretching are carried out can vary within a relatively wide range and depend on the particular composition of the cover layer mixture and on the desired properties of the film.
• the longitudinal stretching is preferably carried out at 90 to 170 ° C and the transverse stretching preferably at 120 to 150 ° C.
• one or both surface (s) of the film can be corona or flame treated by one of the known methods.
• the treatment intensity is generally in the range from 37 to 45 mN / m, preferably 39 to 40 mN / m.
• the procedure is expediently such that the film is passed between two conductor elements serving as electrodes, such a high voltage, usually alternating voltage (approximately 5 to 20 kV and 5 to 30 kHz), being applied between the electrodes that spray or corona discharges can take place.
• a high voltage usually alternating voltage (approximately 5 to 20 kV and 5 to 30 kHz)
• alternating voltage approximately 5 to 20 kV and 5 to 30 kHz
• an electrical direct voltage is applied between a burner (negative pole) and a cooling roll.
• the level of the applied voltage is between 500 and 3,000 V, preferably it is in the range of 1,500 to 2,000 V.
• the applied voltage gives the ionized atoms increased acceleration and impacts the polymer surface with greater kinetic energy. The chemical bonds within the polymer molecule are broken more easily and the radical formation takes place more quickly.
• the thermal load on the polymer is much lower than in the standard flame treatment, and films can be obtained in which the sealing properties of the treated side are even better than those of the untreated side.
• the multilayer film according to the invention is distinguished by a very homogeneous film look, a characteristic matt appearance and excellent scratch resistance.
• the optimized matt surface creates a paper-like appearance of the film, which is particularly desirable in the packaging sector for certain applications.
• the "matt appearance" requirement is met particularly well if the gloss values of the film are below 80 (ASTM-D 523-78), preferably in the range from 10 to 65 (measuring angle 85 °) and the haze (measured in accordance with ASTM D 1003) is in the range from 10 to 80, preferably 30 to 70.
• the multilayer film has excellent printability and a particularly uniform, perfect print image.
• the colors are clear and without a gray haze. There are also no stains or other defects on the printed film.
• the surface tension is surprisingly high and only drops insignificantly even after a storage period of several months.
• the incorporation of resin into the base layer of the film with the top layer according to the invention has advantageous effects on the film properties.
• the resin contributes to a particularly uniform appearance of the film, which surprisingly does not adversely affect the matt appearance. This was particularly surprising since the prior art teaches the resin additive to increase recommend the gloss values.
• the resin significantly improves the scratch resistance of the top layer. This effect on the special top layer composition according to claim 1 was not predictable and also not to be expected without further ado.
• the film is characterized by excellent twist properties.
• the twistability of the film can be described very well by two physical sizes of the film. The greater the permanent elongation (in the longitudinal and transverse direction; measurement method see examples) and the smaller the elongation at break in the longitudinal direction, the better the twistability.
• the values of the above physical quantities should be approximately the same in both directions.
• the ratio of the values for the permanent elongation D bQ : D bL is generally less than 2.0.
• the ratio D bQ : D bL is preferably in the range from 0.5 to 1.5, in particular in the range from 0.7 to 1.3. Corresponding relationships also form the values for elongation at break across and lengthwise.
• the elongation at break like the modulus of elasticity and the tensile strength, is determined in accordance with DIN 53 455.
• the films according to the invention have tensile elongation values in both directions of less than 120%, preferably less than 100%.
• Table 1 Component I Component II I: II B1 C3 homopolymer HDPE + C3 homopolymer 50:50 B2 C2 / C3 copolymer HDPE + C3 homopolymer 50:50 B3 C2 / C3 copolymer HDPE + C3 homopolymer 70:30 B4 C2 / C3 / C4 terpolymer + C3 / C4 copolymer HDPE + C2 / C3 copolymer 60:40 B5 C2 / C3 copolymer HDPE + C2 / C3 copolymer 50:50 B6 C2 / C3 copolymer HDPE + C2 / C3 copolymer 70:30 B7 C2 / C3 copolymer HDPE + C2 / C3 / C4 terpolymer 50:50 B8 C2 / C3 copolymer HDPE + C2 / C3
• a 1 mm thick three-layer film with an XZX layer structure was extruded from a slot die at an extrusion temperature of 220 ° C. H. the base layer Z was surrounded by two identical cover layers X.
• the base layer consisted of a mixture of propylene homopolymer with a nheptane-soluble fraction of 4.5% by weight and a melting point of 165 ° C. and a hydrocarbon resin (a cyclopentadiene resin) with a softening point of 140 ° C.
• the resin content in the base layer was 30%.
• a resin from Exxon (ECR 356) in the form of a 50% masterbatch was used.
• the name of the resin batch was ®Exxelor PA 609.
• the melt flow index of the propylene homopolymer was 3.2 g / 10 min at 230 ° C. and 21.6 N load (DIN 53 735).
• the base layer contained 0.15% by weight of an N, N-bis (hydroxyethyl) - (C10-C20) alkylamine (®Armostat 300) and 0.1% by weight of erucic acid amide.
• Component I consisted of a propylene homopolymer with an n-heptane-soluble fraction of 4.5% by weight and a melting point of 165 ° C.
• the melt flow index of the propylene homopolymer was 6.0 g / 10 min at 230 ° C and 21.6 N load (DIN 53 735).
• Component A consisted of an HDPE with an MFI (50 N / 190 ° C) of 11 g / 10 min (measured according to DIN 53 735), a viscosity number of 160 cm3 / g (measured according to DIN 53 728, part 4), a density of 0.954 g / cm3 (measured according to DIN 53 479, method A), a degree of crystallization of 68% and a melting point of 132 ° C after DSC measurement.
• Component B consisted of a propylene homopolymer with an n-heptane-soluble fraction of 4.5% by weight and a melting point of 165 ° C.
• the melt flow index of component B was 7.0 g / 10 min at 230 ° C. and 21.6 N load (DIN 53 735).
• All layers contained 0.12% by weight of pentaerythrityl tetrakis 4- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (®Irganox 1010) and 0.06% by weight of calcium stearate as neutralizing agent.
• the film was oriented almost isotropically and had an excellent twist behavior.
• the film was also very scratch-resistant.
• the film was approx. 21 ⁇ m thick, the base layer being 19 ⁇ m and each cover layer 100 ⁇ m thick.
• Example 1 was repeated.
• Component I consisted of a statistical ethylene-propylene copolymer with an ethylene content of 5% by weight, based on the weight of the copolymer.
• the melting point of the copolymer was 134 ° C., the melt flow index being 7.0 g / 10 min.
• Example 1 was repeated.
• Component I consisted of a polymer blend of an ethylene-propylene-butylene-1 terpolymer and a propylene-butylene-1 copolymer corresponding to a content of 0.7% by weight of ethylene, 81.3% by weight of propylene and 18% by weight .-% butylene, based on the polymer blend.
• Component A consisted of an HDPE with an MFI (50 N / 190 ° C) of 11 g / 10 min (measured according to DIN 53 735), a viscosity number of 160 cm3 / g (measured according to DIN 53 728, part 4), a density of 0.954 g / cm3 (measured according to DIN 53 479, method A), a degree of crystallization of 68% and a melting point of 132 ° C according to DSC measurement.
• Example 4 was repeated.
• Component I consisted of a statistical ethylene-propylene copolymer with an ethylene content of 5% by weight, based on the weight of the copolymer.
• the melting point of the copolymer was 134 ° C., the melt flow index being 7.0 g / 10 min.
• Component A consisted of an HDPE with an MFI (50 N / 190 ° C) of 11 g / 10 min (measured according to DIN 53 735), a viscosity number of 160 cm3 / g (measured according to DIN 53 728, part 4), a density of 0.954 g / cm3 (measured according to DIN 53 479, method A), a degree of crystallization of 68% and a melting point of 132 ° C according to DSC measurement.
• Component B consisted of a terpolymer of ethylene, propylene and butylene-1 units with an ethylene content of 1.9% by weight and a butylene-1 content of 8.4% by weight, based on the terpolymer .
• Example 5 was repeated.
• Component A consisted of an HDPE with an MFI (50 N / 190 ° C) of 11 g / 10 min (measured according to DIN 53 735), a viscosity number of 160 cm3 / g (measured according to DIN 53 728, part 4), a density of 0.954 g / cm3 (measured according to DIN 53 479, method A), a degree of crystallization of 68% and a melting point of 132 ° C according to DSC measurement.
• Component B consisted of a polymer blend of an ethylene-propylene-butylene-1 terpolymer and a propylene-butylene-1 copolymer corresponding to a content of 0.7% by weight of ethylene, 81.3% by weight of propylene and 18 % By weight of butylene, based on the polymer blend.
• Example 9 was repeated.
• Component I consisted of a terpolymer of ethylene, propylene and butylene-1 units with an ethylene content of 1.9% by weight and a butylene-1 content of 8.4% by weight, based on the terpolymer.
• Example 7 was repeated.
• Component I consisted of a terpolymer of ethylene, propylene and butylene-1 units with an ethylene content of 1.9% by weight and a butylene-1 content of 8.4% by weight, based on the terpolymer.
• Example 1 was repeated.
• Component II consisted of pure HDPE with an MFI (50 N / 190 ° C) of 11 g / 10 min (measured according to DIN 53 735), a viscosity number of 160 cm3 / g (measured according to DIN 53 728, part 4) , a density of 0.954 g / cm3 (measured according to DIN 53 479, method A), a degree of crystallization of 68% and a melting point of 132 ° C according to DSC measurement.
• Example 2 was repeated.
• Component II corresponded to that of Example 12.
• Example 3 was repeated.
• Component II corresponded to that of Example 12.
• Example 11 was repeated.
• Component II corresponded to that of Example 12.
• the melt flow index was measured based on DIN 53 735 at 21.6 N load and 230 ° C or at 50 N load and 190 ° C.
• the viscosity number is a measure of the molecular weight.
• the viscosity number is measured according to DIN 53 728, part 4, in 0.1% decahydronaphthalene solution at 135 ° C.
• the density is determined according to DIN 53 479, method A.
• the haze of the film was measured based on ASTM-D 1003-52.
• the gloss was determined in accordance with DIN 67 530.
• the reflector value was measured as an optical parameter for the surface of a film. Based on the standards ASTM-D 523-78 and ISO 2813, the angle of incidence was set at 60 ° or 85 °. A light beam hits the flat test surface at the set angle of incidence and is reflected or scattered by it. The light rays striking the photoelectronic receiver are displayed as a proportional electrical quantity.
• the measured value is dimensionless and must be specified with the angle of incidence.
• the roughness was determined based on DIN 4768.
• the friction was determined based on DIN 53 375.
• the surface tension was determined using the so-called ink method (DIN 53 364).
• the corona-treated films were printed 14 days after their production (short-term assessment) or 6 months after their production (long-term assessment).
• the color adhesion was assessed using an adhesive tape test. If little color could be removed using adhesive tape, the color adhesion was assessed as moderate and, if the color was clearly separated, poor.
• a 15 mm wide film strip was cut transversely to the machine direction and clamped in a tensile testing machine, the clamping length being 200 mm.
• the sample was then stretched at 20 mm / min corresponding to 10% / min. After an elongation of 10%, ie with a sample length of 220 mm, the sample was automatically released at the same speed. The remaining elongation is calculated according to
• the scratch resistance is determined based on DIN 53 754.
• the Taber model 503 Abraser from Teledyne Taber is used to determine the scratch resistance, using Calibrade R H18 friction wheels that are loaded with 250 g.
• Scratch resistance or scratch sensitivity means the increase in haze of the scratched film compared to the original film after 50 rotations of the sample plate.
• the scratch resistance is rated as very good (+ +) if the increase in turbidity is less than 22%, good (+) if the increase in turbidity is 22 to 25%, moderate ( ⁇ ) if the increase in turbidity is 25 to 30% lies, and with bad (-) with turbidity increases of more than 30%.

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• 1993
  • 1993-04-27 DE DE4313430A patent/DE4313430A1/de not_active Withdrawn
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